SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2021, Vol. 35 ›› Issue (7): 3-16.DOI: 10.1016/j.cjche.2020.08.056

• Review • Previous Articles     Next Articles

Hydroformylation of formaldehyde to glycolaldehyde: An alternative synthetic route for ethylene glycol

Jie Wei, Maoshuai Li, Meiyan Wang, Shixiang Feng, Weikang Dai, Qi Yang, Yi Feng, Wanxin Yang, Cheng Yang, Xinbin Ma   

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
  • Received:2020-07-03 Revised:2020-08-19 Online:2021-09-30 Published:2021-07-28
  • Contact: Maoshuai Li, Xinbin Ma
  • Supported by:
    This work was supported by the National Key Research and Development Program of China (2018YFA0704501).

Hydroformylation of formaldehyde to glycolaldehyde: An alternative synthetic route for ethylene glycol

Jie Wei, Maoshuai Li, Meiyan Wang, Shixiang Feng, Weikang Dai, Qi Yang, Yi Feng, Wanxin Yang, Cheng Yang, Xinbin Ma   

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
  • 通讯作者: Maoshuai Li, Xinbin Ma
  • 基金资助:
    This work was supported by the National Key Research and Development Program of China (2018YFA0704501).

Abstract: Hydroformylation of formaldehyde to glycolaldehyde (GA), as a vital reaction in both direct and indirect process of syngas to ethylene glycol (EG), shows great advantages in the aspects of the process complexity and clean production. The hydroformylation of formaldehyde to GA is thermodynamically unfavourable, requiring the development of highly efficient hydroformylation catalytic systems, appropriate reaction conditions and in-depth understanding of the reaction mechanisms. In this review, we have made a detailed summary on the reaction in terms of the reaction network, thermodynamics, metal complex catalysts (including central metals and ligands), reaction conditions (e.g., temperature, pressure, formaldehyde source and solvent) and promoters. Furthermore, the reaction mechanisms, involving neutral and anionic complex in the catalytic cycle, have been summarized and followed by a discussion on the impact of the crucial intermediates on the reaction pathways and product distribution. A brief overview of product separation and catalyst recovery has been presented in the final part. This review gives new insights into the factors that impact on the formaldehyde hydroformylation and reaction mechanisms, which helps to design more efficient catalytic systems and reaction processes for EG production via the hydroformylation route.

Key words: Formaldehyde, Syngas, Hydroformylation, Glycolaldehyde, Ethylene glycol, Mechanism

摘要: Hydroformylation of formaldehyde to glycolaldehyde (GA), as a vital reaction in both direct and indirect process of syngas to ethylene glycol (EG), shows great advantages in the aspects of the process complexity and clean production. The hydroformylation of formaldehyde to GA is thermodynamically unfavourable, requiring the development of highly efficient hydroformylation catalytic systems, appropriate reaction conditions and in-depth understanding of the reaction mechanisms. In this review, we have made a detailed summary on the reaction in terms of the reaction network, thermodynamics, metal complex catalysts (including central metals and ligands), reaction conditions (e.g., temperature, pressure, formaldehyde source and solvent) and promoters. Furthermore, the reaction mechanisms, involving neutral and anionic complex in the catalytic cycle, have been summarized and followed by a discussion on the impact of the crucial intermediates on the reaction pathways and product distribution. A brief overview of product separation and catalyst recovery has been presented in the final part. This review gives new insights into the factors that impact on the formaldehyde hydroformylation and reaction mechanisms, which helps to design more efficient catalytic systems and reaction processes for EG production via the hydroformylation route.

关键词: Formaldehyde, Syngas, Hydroformylation, Glycolaldehyde, Ethylene glycol, Mechanism